US6121217A - Alkanolamine semiconductor process residue removal composition and process - Google Patents
Alkanolamine semiconductor process residue removal composition and process Download PDFInfo
- Publication number
- US6121217A US6121217A US08/815,616 US81561697A US6121217A US 6121217 A US6121217 A US 6121217A US 81561697 A US81561697 A US 81561697A US 6121217 A US6121217 A US 6121217A
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- 239000000203 mixture Substances 0.000 title claims abstract description 65
- 239000010909 process residue Substances 0.000 title claims description 10
- 238000000034 method Methods 0.000 title abstract description 30
- 230000008569 process Effects 0.000 title abstract description 28
- 239000004065 semiconductor Substances 0.000 title abstract description 15
- 239000010936 titanium Substances 0.000 claims abstract description 38
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims abstract description 36
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 229940074391 gallic acid Drugs 0.000 claims abstract description 18
- 235000004515 gallic acid Nutrition 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 10
- -1 ethylene glycol alkyl ether Chemical class 0.000 claims description 10
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 8
- 239000002738 chelating agent Substances 0.000 claims description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000003495 polar organic solvent Substances 0.000 claims 2
- 229910001069 Ti alloy Inorganic materials 0.000 claims 1
- 150000003609 titanium compounds Chemical class 0.000 claims 1
- 239000002798 polar solvent Substances 0.000 abstract description 7
- 238000009870 titanium metallurgy Methods 0.000 abstract description 7
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 6
- 239000008367 deionised water Substances 0.000 abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 abstract description 3
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 150000004767 nitrides Chemical class 0.000 abstract description 2
- 235000012431 wafers Nutrition 0.000 description 31
- 238000004519 manufacturing process Methods 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 238000004140 cleaning Methods 0.000 description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 229910052681 coesite Inorganic materials 0.000 description 7
- 229910052906 cristobalite Inorganic materials 0.000 description 7
- 238000005530 etching Methods 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 229910052682 stishovite Inorganic materials 0.000 description 7
- 229910052905 tridymite Inorganic materials 0.000 description 7
- 125000002524 organometallic group Chemical group 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000004706 metal oxides Chemical group 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
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- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005360 phosphosilicate glass Substances 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000005389 semiconductor device fabrication Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
- H01L21/02071—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a delineation, e.g. RIE, of conductive layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/103—Other heavy metals copper or alloys of copper
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/20—Other heavy metals
- C23G1/205—Other heavy metals refractory metals
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
- H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31127—Etching organic layers
- H01L21/31133—Etching organic layers by chemical means
-
- C11D2111/22—
-
- C11D2111/24—
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02052—Wet cleaning only
Definitions
- the present invention relates generally to a cleaning composition and process for removal of organic, organometallic and metal oxide residues from substrates. More particularly, it relates to such a composition and process for removing semiconductor device fabrication residues from semiconductor device substrates, such as etching residues after plasma etching processes in the fabrication of integrated circuits on silicon wafers and similar processes. Most especially, it relates to such a composition and process which is effective for the removal of these materials while avoiding substantial attack on metal or insulation layers employed in integrated circuits, including titanium layers.
- Oxygen plasma oxidation is often used for removal of photoresist or other polymeric materials after their use during the fabrication process has been completed. Such high energy processes typically result in the formation of organometallic and other residues on sidewalls of the structures being formed in the fabrication process.
- a variety of metal and other layers are commonly employed in integrated circuit fabrication, including aluminum, aluminum/silicon/copper, titanium, titanium nitride, titanium/tungsten, tungsten, silicon oxide, polysilicon crystal, and the like.
- the use of such different layers results in the formation of different organometallic residues in the high energy processes.
- stripping and cleaning compositions should also not attack the different metallurgies or insulation layers used in integrated circuit fabrication.
- compositions and processes suitable for integrated circuit fabrication have been developed and marketed by EKC Technology, Inc., the assignee of the present application. Some of these compositions and processes are also useful for stripping photoresist, polyimide or other polymeric layers from substrates in integrated circuit fabrication, and EKC has also developed a variety of compositions and processes for stripping such polymeric layers from substrates in integrated circuit fabrication.
- Such compositions and processes are disclosed in the following commonly assigned issued patents: U.S. Pat. No. 5,482,566, issued Jan. 9, 1996 to Lee; U.S. Pat. No. 5,399,464, issued Mar. 21, 1995 to Lee; U.S. Pat. No. 5,381,807, issued Jan. 17, 1995 to Lee; U.S. Pat.
- etching residue removal and substrate compatibility with chemicals employed in wet processing is becoming more and more critical for obtaining acceptable yield in very large scale integration (VLSI) and ultra large scale integration (ULSI) processes.
- VLSI very large scale integration
- ULSI ultra large scale integration
- the composition of such etching residue is generally made up of the etched substrates, underlying substrate, photoresist and etching gases.
- the substrate compatibility of the wafers with wet chemicals is highly dependent on the processing of the polysilicon, multilevel interconnection dielectric layers and metallization in thin film deposition, etching and post-etch treatment of the wafers, which are often quite different from one fabrication process to another.
- Titanium has become more widely used in semiconductor manufacturing processes. It is employed both as a barrier layer to prevent electromigration of certain atoms and as an antireflector layer on top of other metals.
- a residue removal composition in accordance with this invention comprises a two carbon atom linkage alkanolamine compound, gallic acid or catechol, optionally, an aqueous hydroxylamine solution, and desirably a balance of water or another suitable polar solvent.
- a process for removing a residue from a substrate in accordance with this invention comprises contacting the substrate with a composition that contains a two carbon atom linkage alkanolamine compound for a time and at a temperature sufficient to remove the residue from the substrate.
- FIGS. 1-8 are scanning electron microscope (SEM) photographs showing comparative results achieved using the composition and process of the present invention.
- the two carbon atom linkage alkanolamine compounds suitable for use in the invention have the structural formula X, ##STR1## wherein X and Y are, independently in each case, hydrogen, methyl or ethyl, and R is hydrogen or an alkyl group containing from 1 to 4 carbon atoms.
- the two carbon atom linkage alkanolamine compounds useful in the present invention preferably have relatively high boiling points, such as for example, 75° C. or above.
- Preferred specific examples of such two carbon atom linkage alkanolamine compounds include monoethanolamine and monoisopropanolamine.
- the composition desirably contains at least about 10% by weight of at least one two carbon atom linkage alkanolamine compound, from about 5% to about 40% by weight of gallic acid, catechol or other chelating agent, and optionally, up to about 50 percent by weight of a 50% by weight aqueous hydroxylamine solution.
- the balance of the composition is desirably made up of water, preferably high purity deionized water, or another suitable polar solvent.
- the solvents can be used singly or as mixtures.
- the composition preferably includes from about 10% to about 80% by weight of at least one two carbon atom linkage alkanolamine compound, from about 5% to about 30% by weight of the gallic acid or catechol, from about 10% to about 30% of the hydroxylamine solution, with the remaining balance preferably being water or other suitable polar solvent.
- catechol or gallic acid enhances the ability of the two carbon atom linkage alkanolamine compound to remove the residue.
- the presence of the catechol, gallic acid or other chelating agent helps to prevent attack on titanium metallurgy.
- Suitable examples of polar solvents for the composition, in addition to water include dimethyl sulfoxide, ethylene glycol, ethylene glycol alkyl ether, diethylene glycol alkyl ether, triethylene glycol alkyl ether, propylene glycol, propylene glycol alkyl ether, dimethyl sulfoxide, N-substituted pyrrolidone, ethylenediamine and ethylenetriamine. Additional polar solvents as known in the art can also be used in the composition of the present invention.
- the residue cleaning compositions of the present composition are effective in removing organometallic and metal oxide residue from a variety of integrated circuit silicon wafer substrates, including metal layers, such as aluminum or titanium, oxide layers, such as silicon oxides, nitride layers, such as silicon nitride, and the like.
- the cleaning compositions of the present invention are also effective in removing organometallic and metal oxide residue generated on the substrate of etching equipment utilized in the fabrication of integrated circuits. Examples of commercially available etching equipment include that available from Lam Research, Tegal, Electrotech, Applied Materials, Tokyo Electron, Hitachi and the like.
- the method of cleaning a substrate using the cleaning compositions of the present invention involves contacting a substrate having organometallic and metal oxide residue thereon with a stripping and cleaning composition of the present invention for a time and at a temperature sufficient to remove the residue.
- the substrate is generally immersed in the stripping and cleaning composition.
- the time and temperature are determined based on the particular material being removed from a substrate. Generally, the temperature is in the range of from about ambient or room temperature to about 120° C. and the contact time is from about 2 to 60 minutes.
- the substrate may then be rinsed in a polar solvent, such as isopropyl alcohol, followed by a deionized water rinse.
- a polar solvent such as isopropyl alcohol
- the substrate is then mechanically dried, such as with a spin drier, or nitrogen blow dried.
- cleaning compositions according to the present invention suitable for removing resist or other organic residues from a substrate are set forth in
- FIG. 1 is a scanning electron microscope (SEM) photograph of the wafer after this treatment. Substantial undercutting of both Ti layers are visible in this photograph.
- FIG. 2 is a SEM photograph of the wafer after this treatment. No undercutting of the lower Ti layer is visible, and a slight undercutting of the upper Ti layer is visible.
- FIG. 3 is a SEM photograph of the wafer after this treatment. Undercutting of both Ti layers is visible.
- FIG. 4 is a SEM photograph of the wafer after this treatment. A slight undercutting of the lower Ti layer is visible, and no undercutting of the upper Ti layer is visible.
- FIG. 5 is a SEM photograph of the wafer after this treatment. No undercutting of the Ti layer is visible.
- FIG. 6 is a SEM photograph of the wafer after this treatment. No undercutting of the Ti layers is visible.
- FIG. 7 is a SEM photograph of the wafer after this treatment. No undercutting of the Ti layers is visible.
- FIG. 8 is SEM photograph of the wafer after this treatment. Undercutting of the Ti layers is visible.
- compositions B, D, E, F and G successfully remove residues from substrates having a titanium metallurgy while reducing or eliminating attack on the titanium metallurgy.
- Increased amounts of catechol or gallic acid produce an improved reduction of attack on the titanium metallurgy.
- the comparative compositions A, C and H all show substantial attack on the titanium metallurgy, even when a two carbon atom linkage alkanolamine compound is used in the absence of gallic acid or catechol.
- gallic acid or catechol is used with an alkanolamine compound other than a two carbon atom linkage alkanolamine compound, the gallic acid or catechol does not show a similar reduction of attack of the composition on the titanium metallurgy.
- the improved two carbon atom linkage alkanolamine compound based composition and process using such a composition of this invention is suitable for meeting current semiconductor fabrication requirements.
- the composition and process is suitable for removing photoresist residues and other residues from wafers and other substrates including one or more titanium metal layers without substantial attack on such titanium layers.
Abstract
Description
TABLE 1 ______________________________________ Clean- ing Additional Compo- Alkanolamine Gallic Acid/ Hydroxyl- Solvent sition Wt. % Catechol Wt. % Amine Wt. % Wt. % ______________________________________ A 60% DGA 5% Catechol 30% (50 Wt % Aq. Sol'n) B 55% MIPA 10% gallic acid 30% (50 Wt % 5% Water Aq. Sol'n.) C 60% MEA 35% (50 Wt % 5% Water Aq. Sol'n.) D 60% MEA 5% gallic acid 35% (50 Wt % Aq. Sol'n.) E 60% MIPA 5% Catechol 35% (50 Wt % Aq. Sol'n.) F 30% MEA 10% Catechol 30% (50 Wt % 5% Water 25% MIPA Aq. Sol'n.) G 30% MEA 10% gallic acid 30% (50 Wt % 5% Water 25% MIPA Aq. Sol'n.) H 55% DGA 10% gallic acid 30% (50 Wt % 5% Water Aq. Sol'n.) ______________________________________ Abbreviations: DGA = diglycolamine MEA = monoethanolamine
Claims (8)
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
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US08/815,616 US6121217A (en) | 1990-11-05 | 1997-03-11 | Alkanolamine semiconductor process residue removal composition and process |
PCT/US1998/004769 WO1998040453A1 (en) | 1997-03-11 | 1998-03-10 | Alkanolamine semiconductor process residue removal composition and process |
AU66979/98A AU6697998A (en) | 1997-03-11 | 1998-03-10 | Alkanolamine semiconductor process residue removal composition and process |
US09/444,548 US6399551B1 (en) | 1993-06-21 | 1999-11-22 | Alkanolamine semiconductor process residue removal process |
US10/160,035 US6564812B2 (en) | 1990-11-05 | 2002-06-04 | Alkanolamine semiconductor process residue removal composition and process |
US10/442,858 US20040018949A1 (en) | 1990-11-05 | 2003-05-20 | Semiconductor process residue removal composition and process |
US11/785,057 US20080004193A1 (en) | 1990-11-05 | 2007-04-13 | Semiconductor process residue removal composition and process |
Applications Claiming Priority (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/610,044 US5279771A (en) | 1990-11-05 | 1990-11-05 | Stripping compositions comprising hydroxylamine and alkanolamine |
US07/911,102 US5334332A (en) | 1990-11-05 | 1992-07-09 | Cleaning compositions for removing etching residue and method of using |
US7865793A | 1993-06-21 | 1993-06-21 | |
US27314395A | 1995-07-14 | 1995-07-14 | |
US08/523,889 US5672577A (en) | 1990-11-05 | 1995-09-06 | Cleaning compositions for removing etching residue with hydroxylamine, alkanolamine, and chelating agent |
US08/628,060 US6187730B1 (en) | 1990-11-05 | 1996-04-17 | Hydroxylamine-gallic compound composition and process |
US08/815,616 US6121217A (en) | 1990-11-05 | 1997-03-11 | Alkanolamine semiconductor process residue removal composition and process |
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US08/523,889 Continuation-In-Part US5672577A (en) | 1990-11-05 | 1995-09-06 | Cleaning compositions for removing etching residue with hydroxylamine, alkanolamine, and chelating agent |
US08/628,060 Continuation-In-Part US6187730B1 (en) | 1990-11-05 | 1996-04-17 | Hydroxylamine-gallic compound composition and process |
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US09/444,548 Division US6399551B1 (en) | 1990-11-05 | 1999-11-22 | Alkanolamine semiconductor process residue removal process |
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US09/444,548 Expired - Fee Related US6399551B1 (en) | 1990-11-05 | 1999-11-22 | Alkanolamine semiconductor process residue removal process |
US10/160,035 Expired - Fee Related US6564812B2 (en) | 1990-11-05 | 2002-06-04 | Alkanolamine semiconductor process residue removal composition and process |
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US09/444,548 Expired - Fee Related US6399551B1 (en) | 1990-11-05 | 1999-11-22 | Alkanolamine semiconductor process residue removal process |
US10/160,035 Expired - Fee Related US6564812B2 (en) | 1990-11-05 | 2002-06-04 | Alkanolamine semiconductor process residue removal composition and process |
Country Status (3)
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AU (1) | AU6697998A (en) |
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US6221818B1 (en) * | 1990-11-05 | 2001-04-24 | Ekc Technology, Inc. | Hydroxylamine-gallic compound composition and process |
US20040018949A1 (en) * | 1990-11-05 | 2004-01-29 | Wai Mun Lee | Semiconductor process residue removal composition and process |
US20040067860A1 (en) * | 1990-11-05 | 2004-04-08 | Lee Wai Mun | Cleaning compositions and methods of use thereof |
US20040106530A1 (en) * | 2000-04-12 | 2004-06-03 | Jerome Daviot | Inhibition of titanium corrosion |
US20040134873A1 (en) * | 1996-07-25 | 2004-07-15 | Li Yao | Abrasive-free chemical mechanical polishing composition and polishing process containing same |
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US6399551B1 (en) | 2002-06-04 |
AU6697998A (en) | 1998-09-29 |
US6564812B2 (en) | 2003-05-20 |
WO1998040453A1 (en) | 1998-09-17 |
US20020183219A1 (en) | 2002-12-05 |
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